Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D243/00—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms
  • C07D243/06—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4
  • C07D243/08—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4 not condensed with other rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
  • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
  • C07D241/06—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members
  • C07D241/08—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3271—Hydroxyamines
  • C08G18/3293—Hydroxyamines containing heterocyclic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
  • C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
  • C08G18/3848—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing two nitrogen atoms in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
  • C08K5/3462—Six-membered rings

Definitions

• UV light By incorporating a UV light stabilizer in the material.
• Many classes of compounds are known to be useful UV light stabilizers, some being more effective than others.
• Particularly effective 2-keto-diazacycloalkanes which provide stabilized compositions resistant to degradation by UV light include the 2-keto-1,4-diazacycloalkanes disclosed in U.S. Pat. No. 4,190,571; and, the 2-keto-1,5-diazacycloalkanes disclosed in U.S. Pat. No. 4,207,228.
• Other 2-keto-diazacycloalkanes useful as UV light stabilizers are disclosed in U.S. Pat. Nos.
• the compounds of this invention belong to a the general class of compounds known as hindered amines.
• Hindered amines to which general class the compounds of the invention belong, are known to have utility as u-v light stabilizers in synthetic resins subject to actinic radiation.
• not all hindered amines are effective stabilizers against u-v light degradation in normally solid polymers.
• Some hindered amines are thermally unstable at as low as 100° C. which precludes their use in any organic material which is processed at or above that temperature.
• N atoms in the ring are known to have a beneficial effect but there is no logical reason to expect that an oligomer may be formed which has relatively few repeating units of a polyisocyanate which are self-limiting to just about the right number so as to provide a desirable molecular weight; nor is there any reason to expect that a peculiar structure of two distally linked polysubstituted 2-keto-1,4-diazacycloalkane (“2KDZC”) moieties, themselves distally linked, would, in conjunction with a polymeric isocyanate, provide better stabilization activity than either the 2KDZC Bis compound, or the polymeric isocyanate (also termed "urethane oligomer").
• distally linked we refer to bridging or linking by at least 2 carbon atoms.
• Hindered amines of the prior art are generally complex compounds not prepared with notable ease, and their properties, particularly their compatibility in various synthetic resins, is difficult to predict. Apparently small differences in structure, result in large differences in performance. Prolonged efforts to provide simpler compounds which are relatively easily prepared, have resulted in the 2-keto-1,4-diazacycloalkanes and the 2-keto-1,5-diazacycloalkanes disclosed in U.S. Pat. Nos. 4,190,571 and 4,207,228.
• u-v stabilizers include for example, Tinuvin®622 which is a succinate ester of a polysubstituted piperidine, more fully disclosed in U.S. Pat. Nos. 4,233,410 and 4,233,412; Tinuvin®770 which is a triazine substituted with piperidine substituents; and, Chimasorb®944 which has a polytriazine structure with piperidine substituents, as disclosed in U.S. Pat. No. 4,086,204.
• Tinuvin®622 which is a succinate ester of a polysubstituted piperidine, more fully disclosed in U.S. Pat. Nos. 4,233,410 and 4,233,412
• Tinuvin®770 which is a triazine substituted with piperidine substituents
• Chimasorb®944 which has a polytriazine structure with piperidine substituents, as disclosed in U.S. Pat. No. 4,086,204.
• the aforementioned stabilizers are relatively easily extracted from prior art u-v stabilized compositions.
• This invention derives from the discovery that changes in structure of a hindered amine are effective to improve not only the ease with which they may be prepared and thus be inexpensive, but also to improve their extraction from organic polymers, thus giving the polymers longer lasting protection against degradation by u-v light.
• the present invention further derives from research in the field of the synthesis of hindered amines having peculiar structural characteristics, and an evaluation of their effectiveness as u-v light stabilizers.
• the concept of retaining the "2-keto" ring structure of a heterocyclic ring containing at least one N atom was the basis upon which the search for effective polymers containing this structure was initiated.
• the practicality of providing more than two substituents on the N-adjacent C atoms of a 2-keto-1,4-diazacycloalkane derives from the discovery of the "ketoform synthesis" disclosed in U.S. Pat. No. 4,167,512; the "cyanohydrin acetate synthesis" disclosed in U.S. Pat. No.
• Novel compounds have been discovered in which a bis compound of a polysubstituted 2-keto-1,4-diazacycloalkane (“2KDZC”) provides a bridge between diisocyanate groups so as to form an oligomeric 2KDZC-urethane (“2K-U” oligomer) having from 2 to about 15 repeating units. More specifically, the bis compound bridge itself consists essentially of two distally linked polysubstituted 2KDZC moieties.
• a 2K-U oligomer may be formed which consists essentially of two 2KDZC moieties linked through their N 1 atoms, which moieties in turn are distally linked to a urethane through the N 4 atoms of the 2KDZC.
• Such 2K-U oligomers unexpectedly contain a self-limiting number, from about 1 to about 5, of 2K-U repeating units which happens to provide 2K-U oligomers which are desirable and highly effective u-v light stabilizers in organic materials.
• the basic structure of the stabilizer compounds used in stabilized compositions of this invention is a bis compound comprising two polysubstituted 2KDZC moieties linked through their N 1 atoms which bis compound in turn links a urethane group through each of the other N atoms of the diazacycloalkanes.
• the resulting 2K-U oligomer has the structure: ##STR2## wherein, m represents an integer in the range from 0 to 5, being the number of methylene groups forming a bridge of variable length between the ring N atoms, and some of which groups (a) together with the carbons to which they are bound, may form a cyclopentyl, cyclohexyl or cycloheptyl endo ring, or (b) be substituted; so that, when m is 0, the 2KDZC moiety is a piperazinone ring; when m is 1 the 2KDZC moiety is a 5-keto-1,4-diazacycloheptane (referred to herein as a "diazepinone") ring; when m is 4 and cyclized with the other two contiguous C atoms (in the bridge between the N atoms) to form an endo ring, the 2KDZC moiety is decahydroquinoxalinone;
• x represents an integer in the range from 2 to about 15;
• R is selected from the group consisting of alkylene having from 2 to about 12 carbon atoms, toluyl, diphenylmethyl, naphthyl, dimethylbiphenyl, dimethoxy-biphenyl, methylcyclohexyl, dicyclohexylmethyl, xylyl, isophoronyl, trimethylhexyl;
• R 1 , R 2 , R 3 and R 4 are independently selected from the group consisting of hydrogen, aryl, alkyl having from 1 to about 24 carbon atoms, cycloalkyl having from 5 to about 7 carbon atoms, aralkyl having from 7 to about 20 carbon atoms, cyanoalkyl having from 2 to about 12 carbon atoms, ether having from 4 to about 18 carbon atoms, and hydroxyalkyl having from 1 to about 18 carbon atoms;
• R 1 and R 2 together, or R 3 and R 4 together, or each pair, may be cyclized forming a ring having from about 5 to about 8 carbon atoms;
• R 1 , R 2 , R 3 or R 4 may be hydrogen, and no more than three of R 1 , R 2 , R 3 and R 4 may be cyclic;
• R 5 and R 7 are each polymethylene having from 2 to about 12 carbon atoms each of which polymethylene constitutes a connecting link distally connecting a 2-keto-diazacycloalkane moiety to a urethane group;
• R 6 is selected from the group consisting of polymethylene having from 2 to about 12 carbon atoms, xylenyl and substituted or unsubstituted phenyl, which group is a connecting link distally connecting one 2-keto-1,4-diazacycloalkanes moiety to another such moiety.
• these relatively high molecular weight compounds contain a polysubstituted 2KDZC bis compound distally linked to a urethane, and that groups may be independently substituted in both the 2KDZC bis compound or the urethane group, to produce stabilizers having not only desirable uv light stabilizing properties, but also heat stabilizing properties complemented with suitable solubility and dispersability.
• the polysubstituted 2KDZCs together with the urethane group linked thereto are referred to herein as "2K-U oligomers" because they are polymers having from 2 to about 15 repeating units.
• an alkoxylated 2KDZC bis compound may be used as a bridge between urethane oligomers having a self-limiting number of urethane repeating units. If the number were not self-limiting in the range from 1 to about 10, and more preferably in the range from 2 to about 5, the 2K-U oligomer would not be easily dispersable in an organic polymer and therefore be of little use as a u-v stabilizer.
• the self-limiting property of the 2K-U oligomer is attributable to the steric hindrance effects of the substituents on the N 4 atoms of the 2KDZC, and also to the relative impurity of the hydroxyalkylated bis compound which is not especially purified before reacting it with a preselected diisocyanate.
• the polysubstituted 2K-U compounds are generally oils or high melting crystalline solids soluble in acetone, diethyl ether, dioxane, tetrahydrofuran, carbon tetrachloride, chloroform, lower primary alcohols having from 1 to about 5 carbon atoms such as methanol, ethanol and propanol, aromatic hydrocarbons such as benzene and toluene, but much less soluble in aliphatic hydrocarbons such as hexane.
• 2K-U oligomers are generally insoluble in water; they range in color from white to straw-colored when pure.
• the amount of 2K-U stabilizer employed will vary with the particular material to be stabilized and also the particular substituents in the 2K-U employed. Generally however, for effective uv light stabilization of organic materials, an amount of the 2K-U used is in the range from about 0.001 percent to about 10 percent by weight (% by weight) based on the weight of organic material. In typical stabilized compositions the amount of substituted PIP-T used is in the range from about 0.01 to about 5% by weight.
• compositions of this invention are synthetic resinous materials which have been stabilized to combat the deleterious effects of uv light, thermal or oxidative degradation such as are usually evidenced by discoloration and/or embrittlement. These compositions generally benefit from the inclusion of additional, secondary stabilizers to achieve even greater stability against a combination of actinic light, heat and oxygen. Therefore, in conjunction with the stabilizers of this invention, compositions may include stabilizers against degradation by heat and/or oxygen which secondary stabilizers may be present in the range from about 0.1 part to about 10 parts by weight, and preferably from about 0.2 part to about 5 parts by weight per 100 parts by weight of the organic continuous phase.
• Several types of known UV secondary stabilizers may be used, such as those disclosed in U.S. Pat. Nos. 3,325,448; 3,769,259; 3,920,659; 3,962,255; 3,966,711; 3,971,757; inter alia.
• Organic materials which may be stabilized against uv light, thermal and oxidative degradation include copolymers of butadiene with acrylic acid, alkyl acrylates or methacrylates, polyisoprene, polychloroprene, and the like; polyurethanes, vinyl polymers known as PVC resins such as polyvinyl chloride, copolymers of vinyl chloride with vinylidene chloride, copolymers of vinyl halide with butadiene, styrene, vinyl esters, and the like; polyamides such as those derived from the reaction of hexamethylene diamine with adipic or sebacic acid; epoxy resins such as those obtained from the condensation of epichlorohydrin with bisphenols, and the like; ABS resins, polystyrene, polyacrylonitrile, polymethacrylates, poly-carbonates, varnish, phenol-formaldehyde resins, polyepoxides, polyesters, and polyolefin homo- and copoly
• the substituted 2K-U compounds can also be used to stabilize mixtures and blends of polymeric materials such as ABS resin blends, PVC and polymethacrylate blends, and blends of polyolefin homopolymers and copolymers such as blends of polypropylene in epdm polymers.
• polysubstituted 2K-U oligomers of this invention having two polysubstituted piperazinones distally linked together through their N 1 atoms, and again distally linked through their N 4 atoms to urethane groups, so as to form 2K-U oligomers having from 2 to about 15 repeating units.
• Such 2K-U oligomers are especially useful as uv-light-stabilizers for synthetic resinous materials which are at least partially permeable to visible light, and particularly for those which are transparent thereto, such as the polyvinylaromatics and polyolefins.
• Such ingredients include metal oxides such as zinc, calcium and magnesium oxide, fatty acids such as stearic and lauric acid, and salts thereof such as cadmium, zinc and sodium stearate and lead oleate; fillers such as calcium and magnesium carbonate, calcium and barium sulfates, aluminum silicates, asbestos, and the like; plasticizers and extenders such as dialkyl and diaryl organic acids like diisobutyl, diisooctyl, diisodecyl, and dibenzyl oleates, stearates, sebacates, azelates, phthalates, and the like; ASTM type 2 petroleum oils, paraffinic oils, castor oil, tall oil, glycerin and the like.
• metal oxides such as zinc, calcium and magnesium oxide, fatty acids such as stearic and lauric acid, and salts thereof such as cadmium, zinc and sodium stearate and lead oleate
• fillers such as calcium and magnesium carbonate, calcium
• Particularly desirable secondary stabilizers are one or more antioxidants used in the range from about 0.1 part to about 20 parts by weight, preferably from about 0.2 part to about 5 parts by weight per 100 parts by weight of the material.
• antioxidants are phosphite, phosphate, sulfide and phenolic antioxidants, the last being preferred.
• phenolic antioxidants such as 2,6-di-t-butyl paracresol; 2,2'-methylene-bis-(6-t-butyl-phenol); 2,2'-thio-bis-(4-methyl-6-t-butyl-phenol); 2,2'-methylene-bis-(6-t-butyl-4-ethyl-phenol); 4,4'-butylene-bis-(6-t-butyl-m-cresol); 2-(4-hydroxy-3,5-di-t-butylamino)-4,6-bis-(octylthio)-1,3,5-triazine; hexahydro-1,3,5-tris-(3,5-di-t-butyl-4-hydroxyphenyl)-propionyl-s-triazine; hexahydro-1,3,5-tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate; tetrakis[
• the polysubstituted 2K-U stabilizers, and the other compounding ingredients if used, can be admixed with organic materials using known mixing techniques and equipment such as internal mixing kettles, a Banbury mixer, a Henschel mixer, a two-roll mill, an extruder mixer, or other standard equipment, to yield a composition which may be extruded, pressed, blowmolded or the like into film, fiber or shaped articles.
• Usual mixing times and temperatures can be employed which may be determined with a little trial and error for any particular composition. The objective is to obtain intimate and uniform mixing of the components.
• a favorable mixing procedure to use when adding a polysubstituted 2K-U to an organic material is either to dissolve or suspend the compound in a liquid such as hexane or benzene before adding it, or to add the 2K-U directly to the polymeric organic material whether the 2K-U is in the form of a powder or oil, or to extruder-mix the 2K-U and the polymeric material prior to forming the product.
• the u-v stability of a particular composition containing a polymeric material and a polysubstituted 2K-U can be evaluated by exposing a prepared sample of the composition to Xenon or carbon arc light in a Weather-O-meter operating at a temperature of, for example, about 140° F. (60° C.) Degradation of the sample can be followed by periodically measuring tensile strength left, and the hydroperoxide absorption band at 3460 cm -1 or carbonyl absorption band at 1720 cm -1 using an IR spectrophotometer. The rapid formation of carbonyl indicates failure of the sample.
• Samples of u-v stabilized compositions can also be checked for oxidative and thermal stability by measuring the time to discoloration and/or embrittlement of the sample after aging in an air circulating oven at 140° C., and other standard ASTM tests.
• the structure of the compound is confirmed by IR, NMR and mass spectrometer data.
• An analytical sample was obtained by treating the crude product with hot ethyl acetate in which the solid is insoluble, and is isolated by filtration.
• Table I sets forth data obtained in tests conducted with 2 mil thickness samples of polypropylene stabilized with compounds 1-5.
• the blank and each sample includes 0.05 parts per hundred parts of resin ( ⁇ phr ⁇ ) of a tri-functional hindered phenol antioxidant available as Goodrite* 3125, and the amount of stabilizer used in each sample is stated.
• Oven aging is done continuously at 125° C. in the standard test procedure, and the Weather-O-Meter tests give the number of hours after which a sample loses 50% of its tensile strength.

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• 1982
  • 1982-05-06 US US06/375,242 patent/US4455401A/en not_active Expired - Fee Related
• 1983
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